Phenols migration

Bromination can be conveniently effected by transfer of bromine from one nucleus to another. As the Friedel-Crafts isomerization of bromoaromatic compounds generally takes place through an intermolecular mechanism, the migrating bromine atom serves as a source of positive bromine, thus effecting ring brominations (161,162). 2,4,6-Tribromophenol, for example, has been prepared by bromination of phenol with dibromobenzene. 

Various polymers and latexes ai e used in manufacturing different articles for medical use. Safety measures in using such articles require strict control measures which provide for detecting toxic substances on hygienic standard levels or on the permissible migration level (PML) (mg/dm ). Chromatographic reaction methods ai e used to reveal formaldehyde, phenol, and epichlorhydrin. 

If both ortho positions bear substituents other than hydrogen, the allyl group will further migrate to the para position. This reaction is called the para-Claisen rearrangement. The formation of the para-substituted phenol can be explained by an initial Claisen rearrangement to an ortho-2l y intermediate which cannot tautomerize to an aromatic o-allylphenol, followed by a Cope rearrangement to the p-allyl intermediate which can tautomerize to the p-allylphenol e.g. 6 ... 

The key step in this sequence, achieved by exposure of 46 lo a mixture of sulfuric acid and acetic anhydride, involves opening of the cyclopropane ring by migration of a sigma bond from the quaternary center to one terminus of the former cyclo-l>ropane. This complex rearrangement, rather reminiscent of the i enone-phenol reaction, serves to both build the proper carbon. keleton and to provide ring C in the proper oxidation state. 

Semiconducting devices, switches and miniaturised v.h.f. circuits are all particularly sensitive to the slightest reaction on critical surfaces, and in devices calling for the highest levels of reliability even the most inert of the phenolic, epoxide and silicone resins are not considered to be fully acceptablecorrosion of electronic assemblies may often be enhanced by migration of ions to sensitive areas under applied potentials, and by local heating effects associated with current flows. 

One other long-term condition that takes place with relatively low level DC fields in the presence of moisture is the migration of the metal of the conductor into the plastic. This was discovered to be a common thing in the past with silver conductors and phenolic insulators. The first instance of field failures were discovered in telephone equipment. The problem can occur with other metals with phenolic and also conceivably with other plastics that are moisture sensitive and can have a solvating action on the conductor metals that they contact. Most of these type plastics should be avoided inside hermetically sealed containers with movable contacts. Vapors released from the organic plastic deposit on the contacts to produce an insulation layer leading to contact failure. 

Another hydroxylation reaction is the Elbs reaction In this method, phenols can be oxidized to p-diphenols with K2S20g in alkaline solution. Primary, secondary, or tertiary aromatic amines give predominant or exclusive ortho substitution unless both ortho positions are blocked, in which case para substitution is found. The reaction with amines is called the Boyland-Sims oxidation. Yields are low with either phenols or amines, generally under 50%. The mechanisms are not clear, but for the Boyland-Sims oxidation there is evidence that the S20 ion attacks at the ipso position, and then a migration follows. ... 

If both orf/io-positions are substituted, the allyl group undergoes a second migration, giving the >ara-substituted phenol ... 

Plastic foils used for wrapping TLC plates were once reported to contain amides of oleic, stearic, or palmitic acid as antiblocking agents which may migrate from the wrapping material [28]. Similarly, Amos [447] has encountered interferences from contaminants in solvents in the TLC analysis of phenolic AOs in turbine oils. 

The dienone intermediate (53a), as well as enolising to the phenol (52a), is itself capable of undergoing a Cope rearrangement to yield a second dienone (cf. 56a), whose enol is the p-substituted phenol (c/ 57a). Enolisation normally predominates, but where (51) has o-substituents, i.e. (54a), o-enolisation cannot take place, and only the p-phenol (57a) is then obtained. That this product is indeed formed not by direct migration of the allyl group, but by two successive shifts, is suggested by the double inversion of the position of the, 4C label in the allyl group that is found to occur ... 

---